US8999485B2 - Curable liquid silicone rubber composition for forming a sealing member and sealing member - Google Patents

Curable liquid silicone rubber composition for forming a sealing member and sealing member Download PDF

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US8999485B2
US8999485B2 US13/519,300 US201013519300A US8999485B2 US 8999485 B2 US8999485 B2 US 8999485B2 US 201013519300 A US201013519300 A US 201013519300A US 8999485 B2 US8999485 B2 US 8999485B2
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silicone rubber
groups
sealing member
component
hole
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US20130011606A1 (en
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Takayoshi Otomo
Keiji Yoshida
Yuji Saito
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Dow Toray Co Ltd
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Dow Corning Toray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture

Definitions

  • the present invention relates to a curable liquid silicone rubber composition for forming a through hole-containing sealing member and to a through hole-containing sealing member. More particularly, the present invention relates to a curable liquid silicone rubber composition for forming a through hole-containing sealing member, wherein the curable liquid silicone rubber composition can form a silicone rubber that exhibits excellent sealing properties and an excellent resistance to damage in the vicinity of through holes in the silicone rubber sealing member provided by curing. The present invention also more particularly relates to a through hole-containing sealing member comprising a silicone rubber that exhibits excellent sealing properties and an excellent resistance to damage in the vicinity of the through hole.
  • Silicone rubber compositions cure to give silicone rubbers that exhibit a desirable modulus, an excellent heat resistance, an excellent water resistance, and so forth, and for these reasons are used for sealing members such as gaskets, packings, and O-rings.
  • Silicone rubber compositions may be broadly categorized into millable silicone rubber compositions and liquid silicone rubber compositions and into peroxide-curable silicone rubber compositions and addition reaction-curable silicone rubber compositions.
  • Patent Document 1 an addition reaction-curable silicone rubber composition that contains a silicone oil and is intended for gasket applications—refer to JP 05-005064 A (Patent Document 1); a sealing element for waterproof connectors, that is produced from a millable silicone rubber containing a phenylsilicone oil—refer to JP 07-130424 A (Patent of silicone oils—refer to P 2002-338809 A (Patent Document 3) and JP 2004-075813 A (Patent Document 4).
  • Patent Document 1 The silicone rubber composition described in JP 05-005064 A (Patent Document 1) is intended for application to gaskets that are continually immersed in a lubricating oil, and as a consequence the cured silicone rubber product therefrom has an overly high hardness.
  • this silicone rubber composition is molded into a through hole-containing sealing member and, for example, a metal terminal, metal wire, rubber-coated metal wire, or plastic-coated metal wire is repeatedly inserted into the through hole in the air, the silicone rubber around the through hole is prone to become damaged, i.e., an ability to resist damage is not present.
  • the oil bleeding-type sealing element for waterproof connectors described in JP 07-130424 A (Patent Document 2) comprises a millable silicone rubber that contains a phenylsilicone oil and exhibits an excellent surface lubricity.
  • Patent Document 2 the oil bleeding-type sealing element for waterproof connectors described in JP 07-130424 A (Patent Document 2) comprises a millable silicone rubber that contains a phenylsilicone oil and exhibits an excellent surface lubricity.
  • a metal terminal, metal wire, rubber-coated metal wire, or plastic-coated metal wire into the through hole readily causes damage to the silicone rubber around the through hole, i.e., a poor ability to resist damage is exhibited.
  • the oil bleeding-type silicone rubber compositions described in JP 2002-338809 A (Patent Document 3) and JP 2004-075813 A (Patent Document 4) provide cured silicone rubber products that exhibit an excellent surface lubricity.
  • these silicone rubber compositions are molded into a through hole-containing sealing member and, for example, a metal wire, rubber-coated metal wire, or plastic-coated metal wire is repeatedly inserted into the through hole, the silicone rubber around the through hole is prone to become damaged, i.e., the ability to resist damage is inadequate.
  • an object of the present invention is to provide a curable liquid silicone rubber composition for forming a sealing member, wherein the curable liquid silicone rubber composition can form a silicone rubber that exhibits excellent handling characteristics, an excellent sealing performance against water, dust, and contaminated air, and an excellent resistance to damage in the vicinity of through holes, i.e., through-holes in the silicone rubber sealing member provided by curing.
  • An additional object of the present invention is to provide a through hole-containing sealing member comprising a silicone rubber that exhibits an excellent resistance to damage in the vicinity of the through hole, i.e., through-hole, excellent handling properties, and an excellent sealing performance against water, dust, and contaminated air.
  • An additional object of the present invention is to provide a method of manufacturing the aforementioned through hole-containing sealing member.
  • a curable liquid silicone rubber composition for forming a through hole-containing sealing member characterized in that the curable liquid silicone rubber composition comprises
  • a through hole-containing sealing member characterized in that the through hole-containing sealing member comprises a silicone rubber provided by curing a curable liquid silicone rubber composition comprising
  • a liquid silicone rubber base provided by mixing (100-X) weight parts of component (A) with 10 to 100 weight parts of component (B) with the application of heat, X weight parts of component (A), and components (C), (D), (E), and (F) in the amounts specified in [5], wherein X is from 0 (but not including 0) to 30.
  • the curable liquid silicone rubber composition according to the present invention for forming a through hole-containing sealing member can form a silicone rubber sealing member that exhibits excellent handling characteristics, an excellent sealing performance against water, dust, and contaminated air and particularly against water, and an excellent resistance to damage around through holes, i.e., through-holes (for example, the inner wall, entrance opening, and exit opening of the through hole) in the silicone rubber sealing member provided by curing.
  • through holes i.e., through-holes (for example, the inner wall, entrance opening, and exit opening of the through hole) in the silicone rubber sealing member provided by curing.
  • the through hole-containing sealing member of the present invention exhibits an excellent resistance to damage around through holes, i.e., through-holes (for example, the inner wall, entrance opening, and exit opening of the through hole), excellent handling properties, excellent support for the operation of inserting an element or member into the through hole, i.e., through-holes and removing the element or member therefrom, and an excellent sealing performance against water, dust, and contaminated air and particularly with respect to water.
  • through holes i.e., through-holes (for example, the inner wall, entrance opening, and exit opening of the through hole)
  • excellent handling properties for the operation of inserting an element or member into the through hole, i.e., through-holes and removing the element or member therefrom
  • an excellent sealing performance against water, dust, and contaminated air and particularly with respect to water i.e., through-holes and removing the element or member therefrom
  • FIG. 1 is a drawing in side view of a through hole-containing sealing member for use in the traverse/withdraw test in the Examples of the present invention.
  • FIG. 2 is a drawing in side view of a hollow square column 3 fitted with a round metal bar 4 , for use in the traverse/withdraw test in the Examples of the present invention and the Comparative examples.
  • FIG. 3( a ) is a drawing that shows the state in the traverse/withdraw test in which the hollow square column 3 has been inserted into a through hole 2 in a sealing member 1 ;
  • FIG. 3( b ) is a drawing that shows the state in which the hollow square column 3 has traversed the through hole 2 in the traverse/withdraw test;
  • FIG. 3( c ) shows the state after removal of the hollow square column 3 from the through hole 2 in the traverse/withdraw test.
  • This curable liquid silicone rubber composition for forming a through hole-containing sealing member will be described in detail.
  • This curable liquid silicone rubber composition comprises
  • the base component of the composition of the present invention is the liquid organopolysiloxane (A) that is represented by the average unit formula: R a SiO (4-a)/2 wherein R is an unsubstituted monovalent hydrocarbyl group or a halogenated monovalent hydrocarbyl group and a is 1.95 to 2.05, that contains at least two silicon-bonded alkenyl groups in each molecule, and that has a viscosity at 25° C. of 100 to 100,000 mPa ⁇ s.
  • A liquid organopolysiloxane
  • the alkenyl groups in this liquid organopolysiloxane (A) undergo a hydrosilylation reaction with the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane (C), i.e., it cures by crosslinking through an addition reaction.
  • the curable liquid silicone rubber composition according to the present invention is hydrosilylation reaction-curable.
  • This alkenyl group can be exemplified by vinyl, allyl, butenyl, pentenyl, and hexenyl, and is preferably vinyl from the standpoints of ease of production and reactivity in the hydrosilylation reaction.
  • the silicon-bonded organic groups in component (A) other than the silicon-bonded alkenyl groups can be exemplified by alkyl groups such as methyl, ethyl, propyl, and so forth; aryl groups such as phenyl, tolyl, and so forth; and halogenated alkyl groups such as 3,3,3-trifluoropropyl and so forth.
  • alkyl groups such as methyl, ethyl, propyl, and so forth
  • aryl groups such as phenyl, tolyl, and so forth
  • halogenated alkyl groups such as 3,3,3-trifluoropropyl and so forth.
  • methyl is preferably at least 50 mol % and more preferably is 100 mol % of these non-alkenyl silicon-bonded organic groups.
  • component (A) can be, for example, straight chain, partially branched straight chain, or branched chain, with straight chain and partially branched straight chain being preferred.
  • Component (A) has a viscosity at 25° C. of 100 to 100,000 mPa ⁇ s, and, viewed from the standpoint of the molding processability of the silicone rubber composition, preferably has a viscosity at 25° C. in the range from 500 to 50,000 mPa ⁇ s.
  • This liquid organopolysiloxane (A) can be exemplified by dimethylpolysiloxanes endblocked at both molecular chain terminals by dimethylvinylsiloxy groups; dimethylsiloxane.methylvinylsiloxane copolymers endblocked at both molecular chain terminals by dimethylvinylsiloxy groups; dimethylsiloxane.methylvinylsiloxane copolymers endblocked at both molecular chain terminals by trimethylsiloxy groups; partially branched straight-chain organopolysiloxanes comprising the siloxane unit represented by the formula (CH 3 ) 2 (CH 2 ⁇ CH)SiO 1/2 , the siloxane unit represented by the formula (CH 3 ) 2 SiO 2/2 , and the siloxane unit represented by the formula (CH 3 )SiO 3/2 ; organopolysiloxanes as provided by replacing a portion of the methyl groups in the preceding organ
  • the reinforcing silica filler (B) functions to improve the viscosity of the mixture of components (A) and (C) and to improve the mechanical strength of the cured silicone rubber product.
  • This is typically a fumed silica, also known as dry-process silica, or a precipitated silica, also known as a wet-process silica, also known as precipitated silica.
  • organosilicon compound for example, trimethylchlorosilane, dimethyldichlorosilane, hexamethyldisilazane, and octamethylcyclotetrasiloxane. Hydrophobing may also be performed during mixing with component (A).
  • the BET specific surface area of the reinforcing silica filler (B) is preferably 100 to 400 m 2 /g in order to secure a satisfactory improvement in the mechanical strength of the resulting silicone rubber.
  • the curable liquid silicone rubber composition for forming a through hole-containing sealing member contains component (B) in an amount of 10 to 100 weight parts, preferably 20 to 65 weight parts per 100 weight parts of component (A), that is, component (B) is incorporated in an amount of 10 to 100 weight parts, preferably 20 to 65 weight parts per 100 weight parts of component (A) in the composition of the present invention.
  • the organohydrogenpolysiloxane (C) is a crosslinking agent for component (A) and brings about crosslinking of component (A) by the addition reaction between the silicon-bonded hydrogen atoms in this organohydrogenpolysiloxane and the at least two alkenyl groups in component (A).
  • Component (C) has at least two silicon-bonded hydrogen atoms in each molecule, but must contain at least three silicon-bonded hydrogen atoms when component (A) has two silicon-bonded alkenyl groups:
  • component (C) can be exemplified by straight chain, partially branched straight chain, branched chain, network, and dendritic, wherein straight chain, partially branched straight chain, and branched chain are preferred.
  • Component (C) preferably has a viscosity at 25° C. in the range from 1 to 1,000 mPa ⁇ s.
  • the organohydrogenpolysiloxane (C) can be exemplified by dimethylpolysiloxanes endblocked by dimethylhydrogensiloxy groups at both molecular chain terminals; methylhydrogenpolysiloxanes endblocked by trimethylsiloxy groups at both molecular chain terminals; dimethylsiloxane.methylhydrogensiloxane copolymers endblocked by trimethylsiloxy groups at both molecular chain terminals; cyclic methylhydrogenpolysiloxanes; tris(dimethylhydrogensiloxy)methylsilane; tetra(dimethylhydrogensiloxy)silane; partially branched organohydrogenpolysiloxanes comprising the siloxane unit represented by the formula (CH 3 ) 2 HSiO 1/2 , the siloxane unit represented by the formula (CH 3 ) 2 SiO 2/2 , and the siloxane unit represented by the formula (CH 3 )SiO 3
  • organohydrogenpolysiloxanes generated by replacing a portion of the methyl groups in the preceding organohydrogenpolysiloxanes with any selection from non-methyl alkyl groups such as ethyl, propyl, and so forth; aryl groups such as phenyl, tolyl, and so forth; and halogenated alkyl groups such as 3,3,3-trifluoropropyl and so forth.
  • Other examples are mixtures of two or more of the preceding organohydrogenpolysiloxanes.
  • Component (C) is incorporated in the composition of the present invention in an amount that provides from 1.0 to 3.0 moles and preferably from 1.0 to 2.0 moles silicon-bonded hydrogen atoms in component (C) per 1 mole of the alkenyl groups in component (A).
  • the platinum group catalyst (D) is a catalyst that promotes the hydrosilylation reaction between the silicon-bonded hydrogen atoms in component (C) and the silicon-bonded alkenyl groups in component (A) and thereby promotes the cure of the composition of the present invention.
  • Platinum-based catalysts can be exemplified by platinum-based catalysts such as chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, complexes between chloroplatinic acid and a ⁇ -diketone, complexes between platinum and an alkenylsiloxane, platinum tetrachloride, finely divided platinum, solid platinum supported on a support such as alumina or silica, platinum black, olefin complexes of platinum, carbonyl complexes of platinum, and so forth, and by the powder of a thermoplastic organic resin, e.g., methyl methacrylate resin, polycarbonate resin, polystyrene resin, silicone resin, and so forth, that incorporates a platinum-based catalyst as described in the preceding.
  • Rhodium-based catalysts and palladium-based catalysts are other examples of the platinum group catalyst (D).
  • Component (D) is incorporated in the composition of the present invention in a catalytic amount, i.e., component (D) is incorporated in an amount sufficient to bring about the cure of the composition of the present invention, but its quantity of incorporation is not otherwise particularly limited.
  • the quantity of component (D) incorporation is preferably a quantity that provides from 0.1 to 500 weight parts of platinum metal per 1,000,000 weight parts of the composition of the present invention.
  • Component (E) a liquid organopolysiloxane that does not contain an aliphatically unsaturated group, hydrosilyl group, and silanol group, that has a viscosity at 25° C. of 10 to 500,000 mPa ⁇ s, and that is compatible with component (A), functions to improve the damage resistance around the through hole in the sealing member comprising the cured silicone rubber product from the composition of the present invention.
  • Component (E) is non-crosslinking or non-crosslinkable because it does not contain in its molecule an aliphatically unsaturated group, silicon-bonded hydrogen atom, and silicon-bonded hydroxyl group, i.e., silanol group, that is, because it does not contain in its molecule all groups consisting of an aliphatically unsaturated group, silicon-bonded hydrogen atom, and silicon-bonded hydroxyl group.
  • This aliphatically unsaturated group encompasses both alkenyl groups and alkynyl groups.
  • component (E) Compatibility by component (E) with component (A) can be confirmed by no generation of turbidity immediately after the two components have been mixed at ambient temperature and by no separation into two phases after long-term standing at ambient temperature. Since component (E) is compatible with component (A), component (E) remains in a dispersed state in the silicone rubber for long periods and is thus able to continue to manifest its functional effects.
  • the silicon-bonded organic groups in component (E) can be exemplified by alkyl groups such as methyl, ethyl, propyl, and so forth; aryl groups such as phenyl, tolyl, and so forth; and halogenated alkyl groups such as 3,3,3-trifluoropropyl and so forth.
  • component (A) is an organopolysiloxane in which non-alkenyl silicon-bonded groups are methyl groups
  • the silicon-bonded organic groups in component (E) are preferably alkyl groups and particularly preferably are methyl groups.
  • component (A) is an alkenyl-functional dimethylsiloxane.methylphenylsiloxane copolymer
  • the silicon-bonded organic groups in component (E) are preferably methyl groups and phenyl groups.
  • component (E) can be exemplified by straight chain, partially branched straight chain, branched chain, and cyclic.
  • Component (E) is a liquid at ambient temperature and has a viscosity at 25° C. in the range from 10 to 500,000 mPa ⁇ s and preferably in the range from 25 to 250,000 mPa ⁇ s.
  • the reasons for this are as follows: when component (E) has a viscosity below the lower limit on the indicated range, it will then be prone to volatize from the resulting silicone rubber; when, on the other hand, the upper limit on the indicated range is exceeded, the trend of an increasing compression set will appear in the resulting silicone rubber.
  • the organopolysiloxane (E) can be exemplified by dimethylpolysiloxanes endblocked by trimethylsiloxy groups at both molecular chain terminals; methylalkyl(excluding methyl)polysiloxanes endblocked by trimethylsiloxy groups at both molecular chain terminals; dimethylsiloxane.methylalkyl(excluding methyl)siloxane copolymers endblocked by trimethylsiloxy groups at both molecular chain terminals; partially branched straight-chain organopolysiloxanes comprising the siloxane unit represented by the formula (CH 3 ) 3 SiO 1/2 , the siloxane unit represented by the formula (CH 3 ) 2 SiO 2/2 , and the siloxane unit represented by the formula (CH 3 )SiO 3/2 ; dimethylsiloxane.methylphenylsiloxane copolymers endblocked by trimethylsiloxy groups at both molecular chain terminals;
  • Component (E) is incorporated in the composition of the present invention in an amount in the range from 15 to 31 weight % and preferably in the range from 18 to 28 weight %, in each case with respect to the total quantity of components (A), (B), (C), and (E).
  • the reasons for this are as follows: when the quantity of component (E) incorporation is below the lower limit on the indicated range, a trend of declining resistance to damage around the through hole in the silicone rubber sealing member will occur; when, on the other hand, the upper limit on the indicated range is exceeded, a trend of declining mechanical strength and declining tensile modulus for the silicone rubber product will occur, and a trend of declining sealing performance against water, dust, and contaminated air will occur.
  • the previously indicated quantities of component (E) incorporation may not be equal to 10 or less than 10 weight parts per 100 weight parts of component (A).
  • Component (F) a liquid organopolysiloxane that does not contain an aliphatically unsaturated group, hydrosilyl group, and silanol group, that has a viscosity at 25° C. of 10 to 500,000 mPa ⁇ s, and that is incompatible with component (A), is non-crosslinking or non-crosslinkable because it does not contain in its molecule all groups consisting of an aliphatically unsaturated group, silicon-bonded hydrogen atom, and silicon-bonded hydroxyl group, and as a consequence gradually bleeds out from the silicone rubber provided by curing the composition of the present invention and thereby functions to reduce the tack of the silicone rubber surface and improve handling characteristics.
  • component (F) and component (A) can be confirmed by the generation of turbidity immediately after the two components have been mixed at ambient temperature or by separation into two phases after long-term standing at ambient temperature.
  • the silicon-bonded organic groups in component (F) can be exemplified by alkyl groups such as methyl, ethyl, propyl, and so forth; aryl groups such as phenyl, tolyl, and so forth; and halogenated alkyl groups such as 3,3,3-trifluoropropyl and so forth.
  • alkyl groups such as methyl, ethyl, propyl, and so forth
  • aryl groups such as phenyl, tolyl, and so forth
  • halogenated alkyl groups such as 3,3,3-trifluoropropyl and so forth.
  • component (A) is a methylalkenylpolysiloxane
  • the silicon-bonded organic groups in component (F) are preferably phenyl groups and halogenated alkyl groups.
  • component (A) is an alkenyl-functional dimethylsiloxane.methylphenylsiloxane copolymer
  • the silicon-bonded organic groups in component (F) are preferably alkyl groups and particularly preferably are methyl groups.
  • the organopolysiloxane (F) can be exemplified by dimethylsiloxane.methylphenylsiloxane copolymers endblocked by trimethylsiloxy groups at both molecular chain terminals; dimethylsiloxane.diphenylsiloxane copolymers endblocked by trimethylsiloxy groups at both molecular chain terminals; dimethylpolysiloxane endblocked by dimethylphenylsiloxy groups at both molecular chain terminals; dimethylsiloxane.methylphenylsiloxane copolymers endblocked at both molecular chain terminals by dimethylphenylsiloxy groups; dimethylsiloxane.methyl(3,3,3-trifluoropropyl)siloxane copolymers endblocked at both molecular chain terminals by trimethylsiloxy groups; methyl(3,3,3-trifluoropropyl)polysiloxane endblocked at both mole
  • Additional examples are dimethylpolysiloxanes endblocked at both molecular chain terminals by trimethylsiloxy groups; methylalkyl(excluding methyl)polysiloxanes endblocked at both molecular chain terminals by trimethylsiloxy groups; dimethylsiloxane.methylalkyl excluding methyl)siloxane copolymers endblocked at both molecular chain terminals by trimethylsiloxy groups; partially branched straight-chain organopolysiloxanes in which the silicon-bonded groups other than silicon-bonded hydrogen atoms are methyl groups, and comprising the siloxane unit represented by the formula (CH 3 ) 3 SiO 1/2 , the siloxane unit represented by the formula (CH 3 ) 2 SiO 2/2 , and the siloxane unit represented by the formula (CH 3 )SiO 3/2 ; and mixtures of two or more of the preceding organopolysiloxanes.
  • Component (F) is incorporated at from 1.0 to 10 weight % of the sum total of components (A), (B), (C), and (F).
  • the composition of the present invention preferably contains (G) a hydrosilylation reaction inhibitor in order to improve the storage stability by inhibiting gelation and curing at ambient temperatures and in order to make the inventive composition curable upon the application of heat.
  • This hydrosilylation reaction inhibitor can be exemplified by acetylenic compounds, ene-yne compounds, organonitrogen compounds, organophosphorus compounds, and oxime compounds.
  • alkynyl alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, phenylbutynol, 1-ethynyl-1-cyclohexanol, and so forth; ene-yne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-1-hexyn-3-ene, and so forth; and benzotriazole and methylvinylcyclosiloxane.
  • the quantity of incorporation for this hydrosilylation reaction inhibitor is generally in the range from 0.001 to 5, 100 weight parts of component (A) and is preferably in the range from 0.01 to 2 weight parts per 100 weight parts of component (A).
  • the quantity of incorporation of the hydrosilylation reaction inhibitor should be selected as appropriate in conformity with the type of hydrosilylation reaction inhibitor, the properties and content of the hydrosilylation reaction catalyst, the quantity of alkenyl groups in component (A), and the quantity of silicon-bonded hydrogen atoms in component (C).
  • composition of the present invention may contain other optional components insofar as the objects and advantageous effects of the present invention are not impaired.
  • optional components can be exemplified by inorganic extender fillers such quartz powder, diatomaceous earth, aluminum oxide, aluminosilicate, calcium carbonate, and so forth; fillers as provided by treating the surface of an inorganic extender filler with an organosilicon compound; pigments such as iron oxide red, titanium white, and carbon black; agents that improve the compression set, e.g., copper phthalocyanine, chlorinated copper phthalocyanine, and so forth; agents that impart heat resistance, e.g., rare-earth oxides, rare-earth hydroxides, cerium silanolate, and cerium fatty acid salts; flame retardants; agents that impart thermal conductivity; agents that impart electroconductivity; and adhesion promoters.
  • inorganic extender fillers such quartz powder, diatomaceous earth, aluminum oxide, aluminosilicate, calcium carbonate,
  • composition of the present invention can be produced by mixing components (A) to (F) to uniformity or by mixing components (A) to (F) and optional components to uniformity.
  • the composition of the present invention can be prepared by first preparing a liquid silicone rubber base by mixing components (A) and (B) with the application of heat and by then mixing this liquid silicone rubber base to uniformity with components (C) to (F). Or, preparation can be carried out by mixing the liquid silicone rubber base to uniformity with component (A) and components (C) to (F). That is, a liquid silicone rubber base can be produced by mixing (100-X) weight parts of component (A) with 10 to 100 weight parts of component (B) with the application of heat and the composition can then be prepared by mixing this liquid silicone base to uniformity with components (C), (D), (E), and (F) in the amounts specified in claim 1 and X weight parts of component (A) wherein X is from 0 to 30 not including 0.
  • component (B) is a hydrophilic reinforcing silica
  • preparation of the liquid silicone rubber base by mixing components (A) and (B) with the application of heat is preferably carried out with the addition thereinto of an organosilicon compound hydrophobing agent in order to subject the surface of component (B) to an in situ hydrophobing treatment.
  • This organosilicon compound hydrophobing agent can be exemplified by a diorganooligosiloxane endblocked by silanol groups at both terminals, an organoalkoxysilane, a hexaorganodisilazane, trimethylchlorosilane, dimethyldichlorosilane, hexamethyldisiloxane, and octamethylcyclotetrasiloxane.
  • the composition of the present invention can be cured using the usual curing conditions used for curing liquid silicone rubber compositions.
  • the silicone rubber sealing member can be molded by heating the composition of the present invention, for example, for 15 minutes to several minutes at 50 to 250° C. using a prescribed die or mold and a known molding method, e.g., compression molding, injection molding, transfer molding, and so forth.
  • the mold or die is preferably designed to mold, for example, a sheet, slab, disk, and so forth, in each case that has at least one through hole.
  • the through hole-containing sealing member of the present invention can be manufactured by filling the aforementioned liquid silicone rubber composition into a metal mold having a cavity and having at least one pin in the cavity thickness direction, hot pressing the metal mold, and taking out the resulting through hole-containing sealing member made of the silicone rubber.
  • the cavity has a shape being suitable for shaping a sheet, slab, square plate, circular disk, and so forth.
  • the cavity has preferably two or more pins, and, for example, 4, 9, 16, 25, 36, or 49 pins.
  • the shape of each pin cross section should be the same as the cross section of each through hole.
  • the pin has a circular to approximately circular cross section.
  • the cured silicone rubber product from the liquid silicone rubber composition according to the present invention characteristically has a hardness, measured using a type A durometer according to JIS K 6253, “Hardness Test Method for Vulcanized Rubbers”, of 15 to 26 and a tensile stress at 100% elongation, measured according to JIS K 6251, “Vulcanized Rubbers and Thermoplastic Rubbers—Determination of Tensile Properties”, of 0.25 to 0.60 MPa.
  • the silicone rubber sealing member provided by curing exhibits an excellent resistance to damage in and around the through hole, i.e., through-holes precisely because this sealing member contains components (E) and (F) in the specified quantities and has the properties indicated above.
  • a metal terminal, metal wire, rubber coated metal wire, plastic-coated metal wire, and so forth can be easily inserted into this through hole, i.e., through-holes, while the silicone rubber sealing member also resists scratching and damage in and around the through hole, for example, the inner wall, entrance, and exit of the through hole, during repetitive insertion and withdrawal.
  • the infiltration of water, dust, and contaminated air via the through hole opening and along the inserted element is inhibited and an excellent sealing performance is obtained against the preceding and particularly against water.
  • the presence of these functional effects is even more advantageous in those instances in which the through holes are present in large number in a dense configuration.
  • the surface of the silicone rubber sealing member lacks tack, insertion or intercalation between other members and intercalation into various devices are easily performed and the insertability/withdrawability of a member into/from the through holes is also excellent. That is, the assembly workability is excellent.
  • the sealing member according to the present invention is useful as a sealing member for, e.g., electrical devices and equipment, electrical components, electronic devices and equipment, electronic components, and so forth, where waterproofness is required, as are used in, for example, automobiles, vehicles, ships, aircraft, and so forth.
  • this cured silicone rubber product from the curable liquid silicone rubber composition according to the present invention preferably has a tensile strength of at least 2.8 MPa and an elongation of at least 500%, more preferably has a tensile strength of at least 3.0 MPa and an elongation of 500 to 1000%, and most preferably has a tensile strength of at least 3.0 MPa and an elongation of 570 to 900%, in each case as measured according to JIS K 6251, “Tensile Test Methods for Vulcanized Rubbers”.
  • this silicone rubber preferably has a compression set, as measured by the test method described in the examples, of not more than 35%.
  • the through hole-containing sealing member of the present invention is described below.
  • This through hole-containing sealing member of the present invention is formed by curing the previously described curable liquid silicone rubber composition comprising component (A) through component (F) for forming a through hole-containing sealing member of the present invention.
  • This through hole-containing sealing member of the present invention comprises a silicone rubber obtained by curing the previously described curable liquid silicone rubber composition comprising component (A) through component (F).
  • This silicone rubber contains
  • the type A durometer hardness is less than 15 or the tensile stress at 100% elongation is less than 0.25 MPa, a satisfactory sealing performance or capability is not obtained because the stress required for sealing is not fulfilled.
  • the type A durometer hardness exceeds 26 or the tensile stress at 100% elongation exceeds 0.6 MPa, the resistance to damage in and around the through hole in the sealing member is reduced.
  • this cured silicone rubber product from the liquid silicone rubber composition according to the present invention preferably has a tensile strength of at least 2.8 MPa and an elongation of at least 500%, more preferably has a tensile strength of at least 3.0 MPa and an elongation of 500 to 1000%, and most preferably has a tensile strength of at least 3.0 MPa and an elongation of 570 to 900%, in each case as measured according to JIS K 6251, “Tensile Test Methods for Vulcanized Rubbers”.
  • this silicone rubber preferably has a compression set, as measured by the test method described in the examples, of not more than 35%.
  • the through hole-containing sealing member described hereinabove because it contains the two types of liquid organopolysiloxane in the prescribed quantities and has the specific indicated properties, supports facile insertion and withdrawal while resisting damage in and around the through hole—for example, the inner wall, entrance, and exit of the through hole—when, for example, a metal wire, plastic-coated metal wire, rubber-coated metal wire, and so forth, with a somewhat larger diameter than the diameter of the through hole is inserted into and withdrawn from the through hole a large number of times.
  • This through hole-containing sealing member is thereby able to maintain a long-term sealing performance against water, dust, and contaminated air and particularly against water.
  • the surface of the silicone rubber sealing member lacks tack, insertion or intercalation between other members and intercalation into various devices are easily performed and the insertability/withdrawability of a member into/from the through holes is also excellent. That is, the assembly workability is excellent.
  • this through hole-containing sealing member is useful as a sealing member, i.e., a seal, a sealing means, sealing element, for, e.g., electrical devices and equipment, electrical components, electronic devices and equipment, electronic components, and so forth, where waterproofness is required, as are used in, for example, automobiles, vehicles, ships, aircraft, and so forth.
  • this through hole-containing sealing member may be, for example, a sheet, slab, mat, pad, square plate, circular disk, and so forth. At least one through hole is present across its thickness, and at least two through holes are preferred, for example, 4, 9, 16, 25, 36, and 49.
  • the shape of the through hole cross section should be the same or approximately the same as the cross section of the, for example, metal wire, rubber-coated metal wire, or plastic-coated metal wire that will be inserted into the through hole, but is not otherwise particularly limited. Generally, however, the through hole has a circular to approximately circular cross section.
  • the through hole-containing sealing member of the present invention is used in applications where immersion in an oil, for example, a lubricating oil or engine oil, does not occur.
  • Water, dust, and contaminated air and particularly water are typical targets of the sealing action.
  • Examples and comparative examples will be used to provide a detailed description of the inventive curable liquid silicone rubber composition for forming a through hole-containing sealing member and a detailed description of the through hole-containing sealing member of the present invention, which exhibits an excellent resistance to damage in and around the through hole as well as an excellent sealing performance versus water, dust, and contaminated air.
  • the present invention is not limited by the examples.
  • the viscosity reported in the Examples and Comparative Examples is the value at 25° C., while “parts” in the Examples and Comparative Examples denotes “weight parts”.
  • the % value given in parentheses after the dimethylpolysiloxane endblocked by trimethylsiloxy groups at both terminals indicates the % content of this trimethylsiloxy-endblocked dimethylpolysiloxane in the total of components (A) to (F).
  • the liquid silicone rubber composition was cast into a steel mold that had a square cavity with a thickness of 2 mm and a length of 100 mm along a side; press curing was performed for 10 minutes at 150° C. to obtain a 2 mm-thick silicone rubber sheet;
  • the hardness was measured on the aforementioned silicone rubber sheet according to the “Hardness Test Method for Vulcanized Rubbers” of JIS K 6253 using a type A durometer hardness meter.
  • the hardness was measured on the aforementioned silicone rubber sheet according to Standard SRIS 0101 of the Society of the Rubber Industry, Japan, using an Asker type C rubber hardness meter.
  • the compression set was measured in accordance with JIS K 6262, “Compression Set Test Method for Vulcanized Rubbers”.
  • JIS K 6262 “Compression Set Test Method for Vulcanized Rubbers”.
  • the compression set measurement test specimen stipulated in JIS K 6249 was fabricated by curing the liquid silicone rubber composition for 10 minutes at 170° C. After this, the compression set was measured by the method stipulated in JIS K 6249 using compression of the test specimen for 22 hours at 175° C. and a compression rate of 25%.
  • the liquid silicone rubber composition was filled into a steel mold having a square cavity with a thickness of 4 mm and a length of 20 mm along a side and having a centrally located cylindrical pin with a diameter of 0.7 mm and a length of 4 mm in the thickness direction. Curing was performed by hot pressing at a pressure of 20 MPa for 2 minutes at 110° C.
  • the cured product was a square silicone rubber sealing member that had a thickness of 4 mm, a length of 20 mm along a side, and a single cylindrical through hole with a diameter of 0.7 mm.
  • a hollow square column 3 was fabricated by bending a 0.3 mm-thick steel sheet. This hollow square column 3 had a square cross section with a length of 2.5 mm on a side and had a length of 8 mm, and the 2.5 mm-by-2.5 mm square end was open. The hollow square column 3 was fixed at the end of a metal bar 4 that had a diameter of 1.9 mm and was then used in the traverse/withdraw test.
  • the hollow square column 3 for the traverse/withdraw test (refer to FIG. 2 ) was inserted vertically along the longitudinal axis into the 0.7 mm-diameter cylindrical through hole 2 (refer to FIG. 1 ) in the silicone rubber sealing member and, after its complete traverse therethrough, the hollow square column 3 for the traverse/withdraw test was withdrawn vertically along the longitudinal axis of the through hole (refer to FIG. 3 ).
  • One cycle was designated as extending from insertion up to and including withdrawal.
  • the silicone rubber sealing member 1 was sectioned with a razor along the axial direction of the through hole 2 and the depth of the scratching produced by the traverse and withdrawal was observed using a digital microscope; the depth of the scratching was measured at the location at which the deepest scratching occurred.
  • the table reports the depth of scratching (average value) after the traverse/withdraw test had been run 5 times, 10 times, 15 times, and 20 times.
  • the following components were mixed to uniformity in a planetary mixer: 100 parts of a dimethylpolysiloxane endblocked by dimethylvinylsiloxy groups at both terminals and having a viscosity of 50,000 mPa ⁇ s and a vinyl content of 0.08 weight %, 53 parts of wet-process silica having a specific surface area of 200 m 2 /g, 12 parts of hexamethyldisilazane, and 2.4 parts of water. This was followed by treatment by heating for 2 hours at 170° C. while mixing to produce a liquid silicone rubber base A.
  • This liquid silicone rubber base A contained 61 weight % of the dimethylvinylsiloxy-endblocked dimethylpolysiloxane and 39 weight % of hydrophobed silica.
  • the following components were mixed to uniformity in a planetary mixer: 100 parts of a dimethylpolysiloxane endblocked by dimethylvinylsiloxy groups at both terminals and having a viscosity of 50,000 mPa ⁇ s and a vinyl content of 0.08 weight %, 40 parts of dry-process silica having a specific surface area of 280 m 2 /g, 7 parts of hexamethyldisilazane, 0.2 part of dimethylsiloxane.methylvinylsiloxane copolymer endblocked by dimethylhydroxysiloxy groups at both terminals and having a viscosity of 20 mPa ⁇ s and a vinyl content of 11 weight %, and 2 parts of water.
  • This liquid silicone rubber base B contained 68 weight % of the dimethylvinylsiloxy-endblocked dimethylpolysiloxane and 32 weight % of hydrophobed silica.
  • the following components were mixed to uniformity in a planetary mixer: 100 parts of a dimethylpolysiloxane endblocked by dimethylvinylsiloxy groups at both terminals and having a viscosity of 50,000 mPa ⁇ s and a vinyl content of 0.08 weight %, 47 parts of dry-process silica having a specific surface area of 380 m 2 /g, 9 parts of hexamethyldisilazane, 0.2 part of tetramethyldivinyldisilazane, and 1.8 parts of water. This was followed by treatment by heating for 1 hour at 170° C. to produce a liquid silicone rubber base C.
  • This liquid silicone rubber base C contained 64 weight % of the dimethylvinylsiloxy-endblocked dimethylpolysiloxane and 36 weight % of hydrophobed silica.
  • composition number 1 15 parts of a dimethylpolysiloxane endblocked by dimethylvinylsiloxy groups at both terminals and having a viscosity of 50,000 mPa ⁇ s; a dimethylpolysiloxane endblocked by trimethylsiloxy groups at both terminals and having a viscosity of 5,000 mPa ⁇ s (24%); a dimethylsiloxane.methylphenylsiloxane copolymer endblocked by trimethylsiloxy groups at both terminals and having a viscosity of 150 mPa ⁇ s and containing 60 mol % dimethylsiloxane unit and 40 mol % methylphenylsiloxane unit (6%); 2.6 parts of a dimethylsiloxane.methylhydrogensiloxane
  • composition number 2 The following components were added to 156 parts of liquid silicone rubber base A and mixed therewith to uniformity in a planetary mixer to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 2:
  • composition number 3 The following components were added to 156 parts of liquid silicone rubber base A and mixed therewith to uniformity in a planetary mixer to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 3:
  • composition number 4 The following components were added to 156 parts of liquid silicone rubber base A and mixed therewith to uniformity in a planetary mixer to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 4:
  • composition number 6 The following components were added to 144 parts of liquid silicone rubber base B and mixed therewith to uniformity to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 6:
  • composition number 7 The following components were added to 144 parts of liquid silicone rubber base B and mixed to uniformity therewith to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 7:
  • composition number 8 The following components were added to 144 parts of liquid silicone rubber base B and mixed to uniformity therewith to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 8:
  • composition number 9 The following components were added to 144 parts of liquid silicone rubber base B and mixed to uniformity to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 9:
  • composition number 10 The following components were added to 144 parts of liquid silicone rubber base B and mixed therewith to uniformity to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 10:
  • composition number 11 The following components were added to 144 parts of liquid silicone rubber base B and mixed to uniformity therewith to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 11:
  • composition number 12 The following components were added to 144 parts of liquid silicone rubber base B and mixed to uniformity therewith to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 12:
  • this liquid silicone rubber composition will have poor molding properties and a silicone rubber sealing member molded from this liquid silicone rubber composition will not have satisfactory sealing performance or capability.
  • composition number 13 The following components were added to 144 parts of liquid silicone rubber base B and mixed to uniformity to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 13:
  • this liquid silicone rubber composition will have poor molding properties and a silicone rubber sealing member molded from this liquid silicone rubber composition will not have satisfactory sealing performance or capability.
  • composition number 14 The following components were added to 150 parts of liquid silicone rubber base C and mixed to uniformity to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 14:
  • Example 5 Example 6 Example 7 composition number 10 11 12 13 14 liquid silicone rubber base B B B B C dimethylpolysiloxane % 23 30 40 60 0 (E) content methylphenylpoly- % 6 6 5 3 6 siloxane (F) content hardness Asker C 45 35 30 10 40 JIS A 22 16 9 1.8 19 tensile strength MPa 5 3 2.6 0.9 5.9 elongation % 700 598 703 554 850 tear strength N/mm 38 10.3 5.8 1.97 20 tensile modulus (M100) MPa 0.48 0.29 0.21 0.07 0.34 compression set % 30 depth of scratching after the traverse/withdraw test after 5 cycles ⁇ m 13 0 0 0 14 after 10 cycles ⁇ m 64 0 0 75 263 after 15 cycles ⁇ m 59 0 0 0 341 after 20 cycles ⁇ m 61 91 0 0 343
  • composition number 15 a dimethylpolysiloxane endblocked by trimethylsiloxy groups at both terminals and having a viscosity of 50 mPa ⁇ s (30%); a dimethylsiloxane.methylphenylsiloxane copolymer endblocked by trimethylsiloxy groups at both terminals and having a viscosity of 150 mPa ⁇ s and containing 40 mol % methylphenylsiloxane unit (6%); 2.5 parts of a dimethylsiloxane.methylhydrogensiloxane copolymer endblocked by trimethylsiloxy groups at both terminals and having a viscosity of 52 mPa ⁇ s and a silicon-bonded hydrogen atom content of 0.5 weight %; 0.0045 part of a platinum complex of chloroplatinic acid and divinyl
  • composition number 16 a dimethylpolysiloxane endblocked by trimethylsiloxy groups at both terminals and having a viscosity of 100,000 mPa ⁇ s (30%); a dimethylsiloxane.methylphenylsiloxane copolymer endblocked by trimethylsiloxy groups at both terminals and having a viscosity of 150 mPa ⁇ s and containing 40 mol % methylphenylsiloxane unit (6%); 2.5 parts of a dimethylsiloxane.methylhydrogensiloxane copolymer endblocked by trimethylsiloxy groups at both terminals and having a viscosity of 52 mPa ⁇ s and a silicon-bonded hydrogen atom content of 0.5 weight %; 0.0045 part of a platinum complex of chloroplatinic acid and divinyl
  • composition number 17 The following components were added to 144 parts of liquid silicone rubber base B and mixed to uniformity therewith to produce a hydrosilylation reaction-curable liquid silicone rubber composition designated as composition number 17:
  • the silicone rubber sealing member molded from this liquid silicone rubber composition was very tacky and it thus had poor handling characteristics.
  • the surface of the molding had to be covered with a plastic film or sprinkled with talc when the traverse/withdraw test was performed.
  • the operability during insertion and withdrawal of the hollow square column for the traverse/withdraw test was also poor.
  • Example 8 composition number 15 16 17 liquid silicone rubber base B B B dimethylpolysiloxane % 30 30 30 30 (E) content methylphenylpoly- % 6 6 0 siloxane (F) content hardness Asker C 36 35 39 JIS A 16 15 18 tensile strength MPa 3.4 4.1 5.4 elongation % 646 744 768 tear strength N/mm 11 13 33 tensile modulus (M100) MPa 0.31 0.30 0.38 compression set % depth of scratching after the traverse/withdraw test after 5 cycles ⁇ m 0 0 0 after 10 cycles ⁇ m 0 0 0 after 15 cycles ⁇ m 0 0 27 after 20 cycles ⁇ m 0 61 160
  • the through hole-containing sealing member of the present invention is useful for preventing the infiltration of, water, dust, contaminated air and so on, while metal wire, rubber-coated metal wire, plastic-coated metal wire etc. is inserted in the through hole.

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US20130011606A1 (en) 2013-01-10
CA2785683A1 (en) 2011-07-07
JP2011153305A (ja) 2011-08-11
CN102666729B (zh) 2015-01-14

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